CN111192761A - Long-time-state semitransparent flexible dye-sensitized solar cell and preparation method thereof - Google Patents
Long-time-state semitransparent flexible dye-sensitized solar cell and preparation method thereof Download PDFInfo
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- CN111192761A CN111192761A CN201911372306.9A CN201911372306A CN111192761A CN 111192761 A CN111192761 A CN 111192761A CN 201911372306 A CN201911372306 A CN 201911372306A CN 111192761 A CN111192761 A CN 111192761A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a long-time semitransparent flexible dye-sensitized solar cell and a preparation method thereof. The light-facing side of the photo-anode is coated with a dye-sensitized semiconductor porous membrane, the conductive surface of the flexible electrode, which is in contact with the electrolyte, is coated with a polymer transparent electrocatalytic film, and the non-conductive surface is coated with a long-afterglow luminous paint. The preparation process of the battery comprises the following steps: s1, preparing a light-emitting flexible counter electrode: (1) coating a polymer transparent electrocatalytic film, (2) coating a long-afterglow luminous paint film; s2, assembling the long-time semitransparent flexible dye-sensitized solar cell; the battery has high energy conversion efficiency in the daytime, has a certain working effect at night, can realize day and night long-time working of the battery, and has the advantages of simple preparation process, easy operation, easy control and safety.
Description
Technical Field
The invention relates to the technical field of dye-sensitized solar cells, in particular to a long-time semitransparent flexible dye-sensitized solar cell and a preparation method thereof.
Background
The dye-sensitized solar cell is a new third-generation solar cell, and has the advantages of simple preparation, environmental protection, no pollution and relatively high energy conversionThe efficiency is widely concerned by researchers all over the world, and the basic working principle is that the sun light excites the dye to generate electron transition, and the excited electrons are injected into TiO2Nanocrystals while excited dye converts I in electrolyte-Oxidation to form I3 -Electrons are transported to the counter electrode via an external loop, the counter electrode catalyzes I3 -Reduction to I-And completing the cycle.
From the working principle of the dye-sensitized solar cell, the existence of the light source is a precondition for the operation of the dye-sensitized solar cell, however, the dye-sensitized solar cell can only operate in the daytime because of no natural light source at night, which hinders the further use of the dye-sensitized solar cell. If the natural light in the daytime can be reasonably stored to be used as a light source for the working of the dye-sensitized solar cell at night, the working time of the dye-sensitized solar cell can be prolonged as much as possible, and more photo-generated electric energy can be obtained. Chinese patent CN105869894A discloses a dye-sensitized solar cell capable of generating electricity at day and night, which adopts a hard glass substrate, has poor processability, and cannot meet the requirement of flexible devices; and the preparation of the electrocatalytic membrane needs to adopt a more complicated electrochemical deposition mode, so that the preparation cost is high.
Disclosure of Invention
In order to solve the technical problems, the invention provides a long-time semitransparent flexible dye-sensitized solar cell and a preparation method thereof, the cell has high energy conversion efficiency in the daytime and a certain working effect at night, day-and-night long-time work of the cell can be realized, and the preparation method is simple, easy to operate, easy to control and safe.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a long-time semitransparent flexible dye-sensitized solar cell comprises a photo-anode, a luminous flexible counter electrode and semitransparent electrolyte, wherein the photo-anode is opposite to the luminous flexible counter electrode, the semitransparent electrolyte is packaged between the photo-anode and the luminous flexible counter electrode, the light-facing side surface of the photo-anode is coated with a dye-sensitized semiconductor porous membrane, the conductive surface of the luminous flexible counter electrode, which is in contact with the electrolyte, is coated with a polymer transparent electro-catalytic film, and the non-conductive surface is coated with a long afterglow luminous paint film.
The light-emitting flexible counter electrode substrate adopts an ITO conductive film.
The polymer transparent electrocatalytic film is poly 3, 4-ethylenedioxythiophene (PEDOT).
The color of the long-afterglow luminous paint is yellow or green.
The semitransparent electrolyte is a cobalt-based electrolyte.
A preparation method of a long-time semitransparent flexible dye-sensitized solar cell comprises the following steps:
s1, preparing a luminous flexible counter electrode:
(1) coating of a polymer transparent electrocatalytic film:
cleaning an ITO conductive film, drying the ITO conductive film, enabling the conductive surface of the ITO conductive film to face upwards, uniformly and spirally coating the prepared PEDOT polymer mixed solution on the conductive surface of the ITO conductive film, curing the ITO conductive film for 4-6 hours at room temperature, cleaning off attachments on the ITO conductive film, baking the polymer coating on the ITO conductive film, and forming a polymer transparent electro-catalytic film;
(2) coating of the long-afterglow luminous paint film:
the non-conductive surface of the ITO conductive film coated with the polymer catalytic film is faced upwards, the long-afterglow luminous paint is evenly coated on the non-conductive surface in a scraping way, drying is carried out, and a luminous paint film is formed, so that the preparation of the luminous flexible counter electrode is completed;
s2. assembling of solar cell:
fixing the backlight side of the photo-anode on a transparent electro-catalysis film of a luminous flexible counter electrode to enable the photo-anode to be opposite to the functionalized counter electrode, separating the photo-anode from the flexible counter electrode by using a thermoplastic film, injecting a semitransparent electrolyte into a gap between the photo-anode and the flexible counter electrode, and sealing the electrolyte to obtain the long-time semitransparent flexible dye-sensitized solar cell.
In the step S1(1), the ITO conductive film is sequentially cleaned by three solvents of water, acetone and ethanol for 15-25 min in an ultrasonic mode and then dried.
In step S1(1), the deposit on the ITO conductive film is cleaned with ethanol, and then the ITO conductive film is baked at 60 ℃ for 2 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) the flexible ITO conductive film is used as a substrate, so that the prepared long-term battery has a wider application range and can be coated according to the appearance of a building or equipment;
(2) the PEDOT which is easy to prepare, good in light transmission and high in catalytic performance is used as an electrocatalyst of a counter electrode, so that the preparation of a long-time battery is more convenient and controllable, the PEDOT has high adhesion on a flexible conductive film and is not easy to fall off, and the stability of the battery is enhanced;
(3) the semitransparent cobalt-based electrolyte with better light transmittance is used, so that the afterglow of the noctilucent material can be better irradiated on the photo-anode, and the energy conversion efficiency is better than that of the traditional dark iodine-based electrolyte battery;
(4) the long-afterglow luminous paint is used as a luminous light source at night, can store solar energy in the daytime and emit the solar energy in a fluorescent form at night, and provides a light source for a dye-sensitive battery at night; the battery can emit various fluorescent lights at night, and has the functions of decorating and beautifying the environment;
(5) the preparation method is simple, easy to operate and safe, the used raw materials are wide in source and low in price, and the requirements on process conditions and equipment in the preparation process are low.
Drawings
FIG. 1 is a block diagram of the present invention;
FIG. 2 is a graph of transmittance of a flexible counter electrode for preparing a light emitting type;
FIG. 3 is a graph of I-V curves for the daytime operation of preparing a long-time semitransparent flexible dye-sensitized solar cell compared to the daytime operation of a standard dye-sensitized solar cell using platinum electrode compositions;
FIG. 4 is an I-V curve of overnight operation of a long-term semitransparent flexible dye-sensitized solar cell.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
A long-time semitransparent flexible dye-sensitized solar cell comprises a photo-anode, a luminous flexible counter electrode and semitransparent electrolyte, wherein the photo-anode is opposite to the luminous flexible counter electrode, the semitransparent electrolyte is packaged between the photo-anode and the luminous flexible counter electrode, the light-facing side surface of the photo-anode is coated with a dye-sensitized semiconductor porous membrane, the conductive surface of the luminous flexible counter electrode, which is in contact with the electrolyte, is coated with a polymer transparent electro-catalytic film, and the non-conductive surface is coated with a long afterglow luminous paint film.
The light-emitting flexible counter electrode substrate adopts an ITO conductive film.
The polymer transparent electrocatalytic film is poly 3, 4-ethylenedioxythiophene (PEDOT).
The color of the long afterglow luminous paint is yellow or green.
The translucent electrolyte is a cobalt-based electrolyte.
A preparation method of a long-time semitransparent flexible dye-sensitized solar cell comprises the following steps:
s1, preparing a luminous flexible counter electrode:
(1) preparation of poly 3, 4-ethylenedioxythiophene (PEDOT) solution:
dissolving 3, 4-ethylenedioxythiophene monomer 0.6g, polyvinylpyrrolidone 0.2g and pyridine 0.1ml in ethanol 10ml, stirring fully for 2h to obtain solution A, pouring iron p-toluenesulfonate 2g into ethanol 10ml, stirring fully for 2h to obtain solution B, slowly dropping solution B into solution A (for 30 min), sealing the reaction container, and stirring at room temperature (25 ℃) for 24h to obtain PEDOT solution;
(2) coating of PEDOT transparent electrocatalytic film:
sequentially ultrasonically cleaning an ITO conductive film for 20min by using three solvents of water, acetone and ethanol, drying, then placing the ITO conductive film on a spin coater with the conductive surface facing upwards, setting the spin coating speed to be 1000 r/min for 5s, then sucking 200 mul of PEDOT mixed solution by using a liquid transfer gun, dripping the PEDOT mixed solution on the conductive surface of the ITO conductive film, starting spin coating, after the spin coating is finished, placing the ITO conductive film in the air at room temperature (25 ℃) for curing for 4h, then slowly washing by using ethanol to remove surface attachments, then placing the ITO conductive film on a hot platform at 60 ℃ for baking for 2h, and finishing the coating of the PEDOT transparent electro-catalysis film;
(3) coating of the long-afterglow luminous paint film:
the non-conductive surface of the ITO conductive film loaded with the polymer PEDOT catalytic film is faced upwards, then yellow-green luminous paint (water-based energy storage luminous paint, purchased from Shandong Jinan night Brightness science and technology company) is poured on the non-conductive surface, repeatedly blade-coated until a uniform coating is formed, and then placed in the air at room temperature (25 ℃) for 6 hours to form a luminous flexible counter electrode;
s2, preparation of the photo-anode:
adding TiO into the mixture2Photoanode (active area 0.25 cm) of dye-sensitized solar cell formed by loading porous nanocrystal on FTO conductive glass2Purchased from jeans technologies) at 120 ℃ for 2 hours, and rapidly placing the photoanode at 0.3 × 10 when the temperature is reduced to about 80 ℃-3Soaking in mol/L Z907 dye solution in a drying oven at 60 ℃ for 24 hours under the condition of heat preservation to ensure that the dye is fully adsorbed, taking out, cooling to room temperature (25 ℃), washing with absolute ethyl alcohol to remove the unadsorbed dye to obtain a photoanode, and placing the photoanode in a dryer for later use;
s3. assembling the long-state semitransparent flexible dye-sensitized solar cell:
the solar cell is assembled by adopting a sandwich structure, a photo-anode and a counter electrode are bonded together through a thermoplastic film, then semitransparent cobalt-based electrolyte is injected into a gap formed by the two electrodes through a small hole on the photo-anode, the electrolyte is sealed, and the long-time semitransparent flexible dye-sensitized solar cell is simply assembled.
The working principle is as follows: as shown in FIG. 1, under daytime operating conditions, sunlight excites the dye on the anode to undergo electron transition, and the excited electrons are injected into TiO2Nanocrystals while excited dye converts I in electrolyte-Oxidation to form I3 -Electrons are transported to the counter electrode via an external loop, the counter electrode catalyzes I3 -Reduction to I-Completing the circulation; under the working condition at night, the long-afterglow luminous paint on the non-conductive surface of the luminous flexible counter electrode absorbs the solar energy in the daytime, the emitted fluorescence passes through the transparent counter electrode and the electrolyte, the dye on the anode of the excitation light generates electrons, and then the working cycle is completed.
First, transmittance test of light-emitting flexible counter electrode in the invention
The purpose of the test is as follows:
on the premise that the electrolyte is semitransparent, the transmittance of the electrode is the key for determining whether the fluorescent light emitted by the noctilucent material can effectively irradiate the photoanode; if the transmittance of the counter electrode is good, the residual light can effectively penetrate through the counter electrode and the electrolyte and irradiate the photo-anode, so that the photoelectric conversion process is completed, and the current is output.
The test method comprises the following steps:
the prepared ITO conductive film coated with the PEDOT transparent catalytic film is placed in an ultraviolet visible spectrophotometer, a clean blank ITO conductive film is used as a reference substance, the scanning range is set to be 300-800 nm in a visible light region, and the transmittance of the ITO film loaded with the PEDOT catalytic layer is tested.
And (3) test results:
the transmittance of the light-emitting flexible counter electrode is shown in fig. 2, and it can be seen that the transmittance of the PEDOT catalytic film in a visible light region of 300-800 is greater than 45% and can be up to more than 80%, so that the light transmittance of the counter electrode is good, and the residual light can effectively pass through the counter electrode.
Second, the photoelectric conversion efficiency test of the long-term semitransparent flexible dye-sensitized solar cell of the invention
The purpose of the test is as follows:
the prepared novel cell is tested for photoelectric conversion under sunlight conditions and night conditions.
The test method comprises the following steps:
all tests were performed in a night lab with no light source present except the solar simulator. An electrical clip attached to the test instrument was clamped between the photo-anode and the counter electrode of the long-state translucent flexible dye-sensitized solar cell (test cell) prepared in example 1.
When the solar simulator is started, the working state in the daytime is simulated, and the illumination intensity is controlled to be 100mw/cm2The working area of the battery is 0.25cm2A dye-sensitized solar cell (control cell) based on a platinum counter electrode (only the light-emitting flexible counter electrode of the long-state dye-sensitized solar cell prepared in example 1 needs to be replaced by a platinum counter electrode) was used as a control. When the solar simulator is turned off, the working state of the battery at night is simulated because no other light source exists in the laboratory at night.
Testing short-circuit photocurrent (I) of two types of dye-sensitized solar cells (test cell and control cell) in the daytime and nighttime working statessc) Open circuit photovoltage (V)oc) fill factor (ff) and photoelectric conversion efficiency (η), wherein the fill factor refers to the current-voltage product (I) at the point where the maximum output power is obtained in the I-V curveopt×Vopt) And Isc×Voc( IscFor short-circuit photocurrent, VocOpen circuit photovoltage), the electrical conversion efficiency is Iopt×VoptThe ratio of input optical power Pin, where Pin is 25 mW.
And (3) test results:
the I-V curves of the long-term semitransparent flexible dye-sensitized solar cell (test cell) and the dye-sensitized solar cell based on the platinum electrode (control cell) prepared in example 1 during the daytime are shown in FIG. 3, and the short-circuit photocurrent density, the open-circuit photovoltage, the fill factor and the photoelectric conversion efficiency of the test cell are 11.51mA · cm-20.766V, 0.604 and 5.329%, and the short-circuit photocurrent density, open-circuit photovoltage, fill factor and photoelectric conversion efficiency of the control cell were 12.14mA · cm, respectively-20.751V, 0.69 and 6.307%, thus demonstrating that the energy conversion efficiency of the long-term semitransparent flexible dye-sensitized solar cell of the present invention during daytime operation is somewhat different from that of the expensive platinum counter electrode-based dye-sensitized solar cellBut still shows relatively good photoelectric conversion effect.
The I-V curves of the long-time state semitransparent flexible dye-sensitized solar cell (test cell) and the dye-sensitized solar cell based on the platinum counter electrode (control cell) prepared in example 1 in the night operation are shown in the attached FIG. 4, and the short circuit photocurrent density, the open circuit photovoltage, the fill factor and the photoelectric conversion efficiency of the test cell in the night operation are 1.15mA cm respectively-20.1358V, 0.233 and 0.0364%, while the control cell operated at night, the short-circuit photocurrent density, open-circuit photovoltage, fill factor and photoelectric conversion efficiency were 0.0019mA cm-20.01058V, 0.2364 and 1.3X 10-6%, thus, the photoelectric conversion efficiency of the long-state semitransparent flexible dye-sensitized solar cell is far better than that of a dye-sensitized solar cell based on a platinum counter electrode when the long-state semitransparent flexible dye-sensitized solar cell works at night.
From the test results, the long-term semitransparent flexible dye-sensitized solar cell can obtain a photoelectric conversion effect close to that of a platinum counter electrode-based dye-sensitized solar cell when working in the daytime, and under the working condition at night, the fluorescent light emitted by the luminous paint can penetrate through the transparent counter electrode and the semitransparent electrolyte, so that the dye is excited to generate electrons, the day and night long-term working of the dye-sensitized solar cell is realized, and a preliminary research basis can be provided for the design of a subsequent efficient full-time cell.
The above embodiments are merely preferred technical solutions of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A long-time semitransparent flexible dye-sensitized solar cell is characterized by comprising a photo-anode, a luminous flexible counter electrode and semitransparent electrolyte, wherein the photo-anode is opposite to the luminous flexible counter electrode, the semitransparent electrolyte is packaged between the photo-anode and the luminous flexible counter electrode, the light-facing side surface of the photo-anode is coated with a dye-sensitized semiconductor porous membrane, the conductive surface of the luminous flexible counter electrode, which is in contact with the electrolyte, is coated with a polymer transparent electrocatalytic film, and the non-conductive surface is coated with a long afterglow luminous paint film.
2. The long-term semitransparent flexible dye-sensitized solar cell according to claim 1, wherein said light-emitting flexible counter electrode substrate is an ITO conductive film.
3. A long-state translucent flexible dye-sensitized solar cell according to claim 1, characterized in that said polymeric transparent electrocatalytic film is poly 3, 4-ethylenedioxythiophene (PEDOT), the light transmittance of the electrocatalytic film being controlled by spin-on thickness.
4. A long-state translucent flexible dye-sensitized solar cell according to claim 1, characterized in that said long-afterglow phosphorescent paint is yellow or green in color.
5. A long-state translucent flexible dye-sensitized solar cell according to claim 1, characterized in that said translucent electrolyte is a cobalt-based electrolyte.
6. A method of fabricating a long-term, translucent, flexible, dye-sensitized solar cell according to any one of claims 1 to 5, characterized in that it comprises the following steps:
s1, preparing a luminous flexible counter electrode:
(1) coating of a polymer transparent electrocatalytic film:
cleaning an ITO conductive film, drying the ITO conductive film, enabling the conductive surface of the ITO conductive film to face upwards, uniformly and spirally coating the prepared PEDOT polymer mixed solution on the conductive surface of the ITO conductive film, curing the ITO conductive film for 4-6 hours at room temperature, cleaning off attachments on the ITO conductive film, baking the polymer coating on the ITO conductive film, and forming a polymer transparent electro-catalytic film;
(2) coating of the long-afterglow luminous paint film:
the non-conductive surface of the ITO conductive film coated with the polymer catalytic film is faced upwards, the long-afterglow luminous paint is evenly coated on the non-conductive surface in a scraping way, drying is carried out, and a luminous paint film is formed, so that the preparation of the luminous flexible counter electrode is completed;
s2. assembling of solar cell:
fixing the backlight side of the photo-anode on a transparent electro-catalysis film of a luminous flexible counter electrode to enable the photo-anode to be opposite to the functionalized counter electrode, separating the photo-anode from the flexible counter electrode by using a thermoplastic film, injecting a semitransparent electrolyte into a gap between the photo-anode and the flexible counter electrode, and sealing the electrolyte to obtain the long-time semitransparent flexible dye-sensitized solar cell.
7. The method for preparing a long-term semitransparent flexible dye-sensitized solar cell according to claim 6, wherein in step S1(1), the ITO conductive film is sequentially ultrasonically cleaned for 15-25 min by water, acetone and ethanol and then dried.
8. The method for preparing a long-term semitransparent flexible dye-sensitized solar cell according to claim 6, wherein in step S1(1), the ITO conductive film is baked for 2h at 60 ℃ after the attachment on the ITO conductive film is cleaned by ethanol.
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Application publication date: 20200522 |